Liquid cosmetic composition of a two-phase type

ABSTRACT

A two liquid-phase type liquid cosmetic composition of an attractive appearance is provided. The cosmetic composition comprises: (1) oil; (2) an organic liquid miscible with water; (3) water, and; (4) finely divided solid particles insoluble in any of the above ingredients (1), (2) and (3). The oil is dispersed in the form of spheres in a homogeneous mixture of the organic liquid and water. The solid particles are substantially absorbed on the interface between the oil phase and the homogeneous mixture phase of the organic liquid and water.

United States Patent [191 Yamada et al.

[ 51 Nov. 18, 1975 I LIQUID COSMETIC COMPOSITION OF A TWO-PHASE TYPE [75] Inventors: Junichi Yamada, Kamakura; Sanae Kubo, Omiya; Isao Hirano, Yokohama, all of Japan [73] Assignee: Shiseido Co., Ltd., Japan [22] Filed: Nov. 15, 1972 [21] App]. No.: 306,954

[52] US. Cl. 424/78; 424/59; 424/83;

[51] Int. CI. ..A61K 7/02; A61K 7/40;

A61K 31/74; A61K 31/76 [58] Field of Search 424/168, 63, 358, 78

[56] References Cited UNITED STATES PATENTS 3,691,270 9/1972 Charle et a1. 424/168 FOREIGN PATENTS OR APPLICATIONS 1,949,740 7/1970 Germany 424/168 Primar Examiner-Albert T. Meyers Assistant E.\'aminerDale R. Ore

Attorney, Agent, or Firm-Robert E. Burns; Emmanuel J. Lobato; Bruce L. Adams [57] ABSTRACT 4 Claims, 17 Drawing Figures US. Patent Nov. 18, 1975 SheetlofS 3,920,883

Sheet 2 of 5 US. Patent Nov. 18, 1975 US. Patent Nov. 18, 1975 Sheet 4 of5 3,920,883

US. Patent Nov. 18, 1975 Sheet 5 of 5 LIQUID COSMETIC COMPOSITION OF A v TWO-PH ASE TYPE This invention relates to a liquid Cosmetic composition of an attractive appearance; 7 i

In general cosmetics involve both ingredients of oil and water. In order to prepare and emulsion or other uniform dispersion from the-two ingredients immiscible with eath other, nonionic surface active compounds and other surface active compounds haveheretofore been employed as an emulsifier or solubilizer; However, conventional cosmetics having, incorporated therein, these surface active compounds have some of the following disadvantages.

1. Some surface active compounds cause skinor eyelid-irritation or inflammation.

2. Some surface active compounds tend to decompose thereby deteriorating the cosmetics and emitting an offensive odor.

3. When an ingredient other than oil, water and a surface active compound is present in the cosmetic composition, the composition becomes unstable, which leads to phase separation. This is a frequent'phenomenon in the employmentof most-surface active compounds. Accordingly, it is very difficult to find a suitable surface active compound. 'i i 4. Surface active compounds cause undesirable foaming in cosmetics such as hair tonic and face lotion. This phenomenon is anything but agreeable.

5. Most surfaces active compounds diminish the effects of antiseptic, colorant and perfume components.

6. Even when a surface active compound is employed, the amount of oil'capable of beingincorporated into the cosmetic is restricted, i 'e'. it is difficult to obtain a liquid cosmetic composition rich in oil.

In order to minimize these troubles, a cosmetic: has been proposed which contains a very'limite'd amount of a surface active compound. This'cosmetic comprises two different liquid phases, iLe. an oilyv phase and an aqueous phase, separated above and below because of insufficient capability of forming a homogeneous -mi xture. Obviously, such an above and below separated two phase type liquid cosmetic is inferior in capability, of being readily mixed into a homogeneous mixture by shaking. Therefore, when the cosmetic 'is repeatedly used, the upper oily portion initially tends to be consumed in an amount larger'than that of the below aque ous phase. Further, since the cosmetic contains a suravoided. V

Some conventional liquid cosmetics contain waterinsoluble finely divided solid particles- However, these also need the incorporation of a surface active compound to impart the capability of the solid, particles.

exhibits improved capability of readily forming a substantially homogeneous mixture by shaking, although the liquid cosmetic composition contains no surface active compound, and also exhibits an improved capability of being readily restored to the original state after the use.

Still another object of the present invention is to provide a liquid cosmetic composition having an attractive appearance.

A further object of the present invention is to provide a liquid cosmetic composition which can be prepared from a great variety of oils and oily materials.

Other objects and advantages of the present invention will be apparent from the following description.

In accordance with the present invention, there is provided a liquid cosmetic composition of two phase liquid type comprising:

(1) oil; (2) an organic liquid miscible with water; (3) water and; (4) finely divided solid particles insoluble in either of said oil, organic liquid and water and having an average particle size of no greater than 100 1.. Said oil is dispersed in the form of spheres in a homogeneous mixture of said organic liquid and water. Said finely diyided solid particles are adsorbed on the interface between said oil and said homogeneous mixture of said organic liquid and water.

The liquid cosmetic composition of the present invention comprises two different liquid phases. One phase is a homogeneous mixture of an organic liquid, and water, The organic liquid is miscible with water but I is substantially immiscible with oil. The other phase is sands or more per litre of the liquid cosmetic composition. The diameter of the oil spheres range from 0.1

mm to several centimeters.

The liquid cosmetic composition of the present invention has the following advantages:

1. This liquid cosmetic composition contains no surface active agent and, therefore, it is possible to avoid the troubles caused by a surface active agent as set forth above. 2. Although this liquid cosmetic composition contains no surface active agent, it exhibits capability over face active compound, .even though only. a minor] amount, the troubles listed above cannot be completely being uniformly dispersed by shaking. Unless a, surface active compound is incorporated into this type of liquid cosmetic, the solid particles inevitably form a precipitate or coagulation. Therefore, these conventional liquid cosmetics also have the disadvantages setnforth have the disadvantages caused by a surfaceactive com pound, as set forth above.

conventional liquid cosmetics of forming a substantially homogeneous mixture when shaken by hand at the time of use.

persionof oil spheres in the aqueous phase is stable.

It has been found that the state of oil spheres dispersed the aqueous phase is not varied even after Another object of the present inventionjs to provide a two-phase type liquid-cosmetic composition which being infsettled storage over a period of 3 years.

I This liquidcos'metic composition exhibits improved capability of readilyforming a substantially homogeneous mixture when shaken at use, as compared to a conventional above and below separated two phase type liquid cosmetic. Further, the liquid cosmetic composition also exhibits improved capability of being readily restored to the orginal state after the use.

5. The finely divided solid particles in the liquid cosmetic composition suppress the underside glare resulting from the oil ingredient at the time of use. Further, the solid particles exhibit a skin-astringent effect and a sunlight-screening effect. When a medicine is absorbed on the solid particles, the resulting particles have a medicinal effect.

6. The liquid cosmetic composititon is of an attractive appearance. Oil spheres dispersed in the aqueous phase may be transparent, translucent or pearl-like in appearance. These may possess any color. The size and the number of the oil spheres may be varied Therefore, a great variety of cosmetic can be provided. This is obviously advantageous from the viewpoint of merchandizing, because these liquid cosmetic can be distinguished according to the intended use. For example, liquid cosmetics containing a relatively large number of oil spheres can be readily recognizable as being for a dry skin use while those of a relatively small number of oil spheres for a normal skin, and so forth.

Oils used in the present invention are those which are liquid at room temperatures, immiscible with water, and have a specific gravity smaller than that of water. For example, oils include preferably high-molecular weight hydrocarbons such as liquid paraffin (a hydrocarbon oil consisting mainly of alkyl naphthene), squalane (2, 6, l0, l5, l9, 23-hexamethyltetracosane) and the like; monoor di-esters of fatty acid such as 2-hexyldecyl palmitate, 2-octyldodecyl myristate, di-2-hexyldecyl adipate, di-Z-ethylhexyl sebacate and the like; vegetable and animal oils, i.e. triglycerides of fatty acid, such as olive oil, tsubaki oil, mink oil and the like; higher fatty acids having to 25 carbon atoms such as isostearic acid, oleic acid and the like; fatty alcohols having 10 to 25 carbon atoms such as oleyl alcohol; and synthetic oils such as silicone oil, polyalkylene glycol derivatives and the like. The polyalkylene glycol derivatives include, for example, Unilube MB-37O (Bu-O+CH(CH )-CH O+,,H, n=40, trade name made by NIHON YUSHI K. K., Japan). These oils can be used either alone or in a combination of at least two. Oily solid substances such as wax, i.e. an ester of a highmolecular weight fatty acid with a high-molecular weight fatty alcohol, and fat, i.e. a triglyceride of a high-molecular weight fatty acids, may be dissolved in the oil used in the present invention.

The amount of oil present in the liquid cosmetic composition may be varied within the range of lower than approximately 95% by weight, preferably lower than 60% by weight.

Finely divided solid particles used in the present in; vention are those which have an average particle size of below approximately lOOu, are pharmaceutically nontoxic to the skin, and insoluble in both oil and the homogeneous mixture of water and the organic liquid. Preferable finely divided solid particles include those of, for example, natural inorganic substances such as talc, kaolin, and the like; artificial inorganic substances such as iron oxide, magnesium oxide, zinc oxide, zinc peroxide, titanium oxide, calcium carbonate (prepared and precipitated), calcium secondary phosphate, aluminum hydroxide, antimony oxide, alumina, barium sulfate; inorganic pearl-like substances (bismuth oxychloride, titania), silicic acid anhydride, magnesium metasilicate aluminate (MgO'Al O 2SiO silicaalumina, and the like; natural organic substances such as protein, microcrystalline cellulose, fish scale, pearl and the like; and artificial organic substances such as high polymeric substances, e.g. polyvinyl chloride, nylonl 2 (poly-Qlauryllactam HlNH(CH ,-CO ,,OH), and the like; organic pigments and lakes, e.g. Permanent Orange (see Colour Index, Pigment Orange 5, 12075) and Lithol Rubine BCA (Trade name, made by BASF, Germany). These finely divided solid particles may be coated with suitable substances such as, for example, metal soaps, surfactants and polymers. These solid particles may be used either alone or in combination.

The amount of the finely divided solid particles present in the liquid cosmetic composition may be varied within the range of lower than approximately 50% by weight.

Organic liquids used in the present invention are pharmaceutically non-toxic to the skin, and miscible with water, but substantially immiscible with the oil set forth above. The organic liquids may be either completely immiscible, or slightly miscible with the oil if the homogeneous mixture of the organic liquid with water is immiscible with the oil. Further, the organic liquid has in usual a specific gravity of lower than 1.0.

The organic liquid include, for example, monohydric alcohols having carbon atoms of no greater than 5 such as ethyl alcohol, isopropyl alcohol and tetrahydr-ofurfuryl alcohol; polyhydric alcohols such as those having carbon atoms of no greater than 6, for example, propylene glycol, glycerin, sorbitol, dipropylene glycol, 1,3- butylene glycol and mannitol, and polyethylene glycol having carbon atoms of no greater than 50; ethers having carbon atoms of no greater than 6 such as 'diethylene glycol ethyl ether, ethyl ether, dioxane and tetrahydrofuran; ketones having carbon atoms of no greater than 6 such as acetone and N-methylpyrrolidone. Of these organic liquids, ethyl alcohol, isopropyl alcohol and N-methylpyrrolidone are most preferable.

The homogeneous mixture of water and the organic liquid present in the liquid cosmetic composition may be varied within the range of lower than approximately by weight.

In the liquid cosmetic composition of the present invention, oil ingredient, in the fonn of small spheres, are dispersed in a homogeneous mixture of water and the organic liquid. in order to prepare the stable dispersion of the oil spheres in the homogeneous mixture of water and the organic solvent, the following prerequisites should be satisfied.

V l. The difference in specific gravity between the oil ingredient (d and the homogeneous mixture (d of water and the organic liquid is zero or nearly zero.

- 2. Spreading coefficient (S) defined by the followingequation is negative.

wherein -y,, is a surface tension of the oil ingredient, 7,, is a surface tension of a homogeneous mixture of water and the-organic liquid, and 7 is an interfacial tension between the oil ingredient and the homogeneous mixture of water and the organic liquid.

If spreading coefficient is zero or positive, oil spheres break, when buoyed up to the surface, to form an above and below separated two-phase type liquid. This two-phase liquid is not restored to the original state.

3. Oil and the homogeneous mixture are immiscible with each other.

In order to balance the specific gravity between the oil and the homogeneous mixture of water and the organic liquid,.the particular organic solvent to be mixed with water and the proportion of the amount thereof to the amount of water should be suitably determined depending upon the specific gravity of the particular oil used. For example, when a liquid paraffin having a specific gravity of (1 0.8470 is employed as an oil ingredient, a homogeneous mixture of the same specific gravity can be prepared by blending 25% by weight of water and 75% by weight of ethyl alcohol having a specific gravity of d; 0.7808.

When finely divided solid particles having a relatively large particle size, i.e. l0p.l00p., are employed, the specific gravity should preferably be completely balanced between the oil and the homogeneous mixture of water and the organic liquid. However, the smaller the particle size of the solid particles, the greater the warrantable difference in specific gravity between the oil and the homogeneous mixture.

In one modified embodiment of the liquid cosmetic composition of the present invention, the liquid cosmetic composition is composed of oil, an organic liquid miscible with water and finely divided solid particles, i.e. water can be omitted from the cosmetic composition, if the prerequisites set forth above are satisfied, as exemplified in Example 1 below.

Further, the following factors should preferably be taken into consideration for ensuring good dispersibility when shaken, good reproducibility of the dispersion after shaking is stopped and a reasonably high reproduction speed of the dispersion after shaking is stopped.

The dispersibility when shaken depends upon the interfacial tension between the oil and the aqueous mixture, the viscosity of the oil and the shaking force. Reproducibility of the dispersion after shaking is stopped depends upon the joining speed of oil spheres dispersed, the polarity of oil, the miscibility between oil and the aqueous mixture, and the solubility between oils when two or more oils are employed. Reproduction speed of the dispersion after shaking is stopped depends upon the joining speed of oil spheres, the difference in specific gravity between oil and the aqueous mixture, the temperature, and the viscosity of the aqueous mixture.

The relationship between physical characteristics of finely divided solid particles and the shape of the oil spheres dispersed in the homogeneous mixture of water and organic liquid will be illustrated with reference to the accompanying drawings.

FIGS. 1A and 1B show model pictures of the microscopic photograph of the interfacial portion between the oil phase and the aqueous phase consisting of a homogeneous mixture of water and the organic liquid, and the appearance of the waterorganic liquid-solid particles-oil system, respectively, when hydrophilic, finally divided solid particles are employed.

FIGS. 2A and 28, 3A and 3B, and 4A and 4B, show similar model pictures when slightly hydrophilic,

slightly oleophilic and oleophilic, finely divided solid particles are employed, respectively.

As shown in FIGS. 1A and 1B, when the finely divided solid particles employed are hydrophilic, the particles 1 are dispersed in an aqueous liquid phase 2, but not in an oil phase 3, and gradually settle to the bottom of the aqueous liquid phase 2 to form a sediment 4. Therefore, hydrophilic solid particles are unsuitable for the provision of the cosmetic composition of the present invention.

When the solid particles are slightly hydrophilic, these solid particles 1 are adsorbed on the interface of oil spheres 3 and thereby the oil spheres 3 are stably dispersed in an aqueous phase 2, as shown in FIGS. 2A and 2B. The number and the size of the oils sphere 2 may be varied depending upon the amount of the solid particles employed.

When the solid particles are slightly oleophilic, the solid particles 1 are adsorbed on an inside of the surface of oil spheres 3, and the oil spheres 3 are unstable and tend to unite with each other, as shown in FIGS. 3A and 3B. The united oil sphere 3' exhibits an intricate shape and a creased surface with wrinkles. Therefore, finely divided solid particles should preferably possess a hydrophilic property slightly stronger than or well-balanced with an oleophilic property.

When the solid particles are oleophilic, these particles 1 are dispersed within an oil sphere 3, as shwon in FIGS. 4A and 4B.

Hydrophilic characteristics of the solid particles may be expressed in terms of a sedimentation volume per unit of apparent specific volume (hereinafter referred to as fw for brevity) of the solid particles in water, or a hydrophilic coefficient of the solid particles.

When finely divided hydrophilic solid particles are dispersed in water, these particles form a relatively uniform dispersion. In contrast, when finely divided oleophilic solid particles are dispersed in water, these particles do not form a uniform dispersion but partially coagulate. In other words, in water the hydrophilic solid particles exhibit a small sedimentation volume, but the oleophilic solid particles exhibit a large sedimentation volume. Therefore, fw may be one of the yardsticks for determining the hydrophilic property. The fw in water is represented by the formula:

fw=sedimentation volume in water (in cc/g)/apparent specific volume (in cc/g) The sedimentation volume in water and the apparent specific volume are determined as follows.

I. Sedimentation volume A finely divided solid particle specimen is heated at C for 2 hours, cooled, and then weighed. The specimen is dispersed in an aqueous 20% ethyl alcohol solution. After the dispersion is deaired by vacuuming at a pressure of 4 to 5 mmI-Ig, the dispersion is settled in a settling tube over a period of one month. Then, the sedimentation volume is measured.

2. Apparent specific volume A finely divided solid particle specimen is heated, cooled and weighed in the same manner as described above. A slender glass tube is then filled with approximately 20 g of the specimen. After that, the glass tube is repeatedly dropped 400 times from a height of 4 cm. Then, the apparent specific volume is measured.

Sedimentation volume, apparent specific volume and fw of some finely divided solid particles are exemplified in Table l.

Table I Table II Sedimenta- Apparent Specific N 5011C! PflrIiClC SII:0 2 Solid particle tion volume specific (m /g) /g) N .2

0 .7- wlume 5 1 COllUldLll kaolin 11.3 17.0 1.50 9 2 Mica 8.6 12.0 1.40 l Anhydrous 3 Calcium carbonate.

silicic A 4.33 12.20 0.35 2.441 4 f f i a 33 acid 2 B 15.37 15.90 0.97 2.774 5 Qflg dioxide 1H 3 CV] C 3'576 anatasc 8.9 9.0 1.01 7 6 Yellow iron oxide 25.3 25.1 g 0.99 l 7 Zinc flower A 4.8 4.5 0.94 5 Culclum 8 Zinc flower B 4.4 3.0 0.68 fq 1460 9 Zinc lauratc 3.6 2.8 0.78 P p i0 Tale A 4.1 2.3 0.56 6 Calcium 11 Carbon black 215.8 97.7 0.45

carbonate. 1 26 1.22 1.03 2.676 15 prepared 7 Titanium dioxide. 1.71 1.19 1.44 4.080 The relationship between hydrophilic coefficient "1 (S /S and sedimentation volume in water er unit 8 Titanium 2 2 dioxide "90 I 27 L50 3 783 of apparent specific volume (fiv) is shown in FIG. 5. anatase Numerical references indicated in FIG. 5 correspond to 9 m l those of specimens shown in Table II. As apparent from IOXI C (particle Size 521 680 077 3430 FIG. 5, 5 /S and fw exhibit a negative interrelation- 30 my.) ship. 5' A H7 5-715 The relationship between specific gravity and fw is O\\'Cl' H Zinc 170 H7 2 3 5528 shown in FIG. 6. Finely divided solid particles having a flower B specific gravity and an fw, both falling within the area 17 7 41 090 7 68 4444 expressed with hatching in FIG. 6 are preferably eminc PEI'OXI e l3 Talc A 3480 "79 212 1612 ployed for the preparation of the liquid composition of 14 Talc B 3.30 2.08 1.57 2 779 the present invention. FIG. 6 has been drawn on vari- ;2 8-2: ous solid particle specimens in the case where a di-2- l J hexyldecyl adipate-water-ethyl alcohol comb1nat1on 17 lnor ZlnlC 1.84 1.54 1.19 2.801 was em 10 ed. However, a similar tendenc has been g Pearl g observed in the case where other combinations were 18 Bentonitc 1.70 0.95 1.79 2.235 19 Alumina 0.31 1.02 0.30 1.826 employed 20 Pearl (3111C 2.37 1.72 1.38 2.618 With reference to the above considerations, finely 3i a lf 12: 2;: 22:; divided solid particles suitably employed in the present fig invention will be easily chosen. Preferable solid parti- 23 Mica 2.17 1.83 1.19 2 789 cles depend upon the particular oil and the particular 34 M S 16 7 67 l 97 7 719 liquid miscible with water. For example, finely divided 40 solid particles having an fw falling within the range of 25 Yellow 12.28 4.70 2.61 3.539 0.5 to 3.5 are suitable for the combination ofliquid par- 6 gpn fxiae 4 99 I 00 499 4 887 affin and an aqueous ethyl alcohol solution of a 78% concentration. When finely divided solid particles do 27 Bismuth .37 1.05 2.26 3.618 not have an fw falling within the above range, a stable 78 g f 7 73 3 99 l 94 I 73 liquid composition wherein oil spheres are dispersed is 5 g gs not obtainable. That is, the solid particles settle down, micro- 5.72 1.90 3.01 1.412 and the oil phase and the aqueous phase separate from 30 g l 7 94 7 04 l 44 1 mg each other above and below. Otherwise, the liquid 3] gg 5: Z566 composition becomes cloudy, or oil spheres dispersed Orange in the aqueous phase tend to be incorporated with each 32 Carbon black 10.32 5.40 1.91 th 3 1. 4 7 29 1.782 3 e BCA 3 76 6 The number and size of oil spheres dispersed in the 34 Polyvinyl 1.37 a 1.460 aqueous phase can be easily varied by controlling the chloride amount of finely divided solid particles and oil em- Nole: Determined on specimen after heating at 105C for 2 hours.

the greater the hydrophiliqproperty of the solid particles.

Hydrophilic coefficient of some finely divided solid particles are exemplified in Table II.

ployed. The size of oil spheres may be varied within the range of 0.1 mm to 1.0 cm or more, preferably 1.0 mm to 5.0 mm, as expressed in diameter.

The manner of preparation of the two-phase type liquid cosmetic composition of the present invention is not critical. Four ingredients, oil, water, the organic liquid and finely divided solid particles may be blended with each other concurrently or sequentially in any or-- der, by using a conventional blending device. However, the liquid cosmetic composition is preferably prepared in the following manner. First, water and the organic liquid miscible with water are mixed with each other to prepare the homogeneous mixture. followed by the addition of finely divided solid particles. Then, oil is 9 added to the mixture followed by agitation. The resulting mixture is left to settle over a stated period, e. g. one day..

The two-phase type liquid cosmetic composition of the present invention may contain additives such as, for example, colorant, perfume, antioxidant, ultraviolet ray absorber, antiseptic, wetting agent, astringent, or other cosmetic base. The liquid cosmetic composition has a wide variety of uses as hair or skin cosmetics such as hair tonic or lotion, skin lotion or toilet water.

The invention will now be illustrated with reference to Examples. In the Examples, all parts are parts by weight.

EXAMPLE 1 EXAMPLE 2 55.51 parts of ethyl alcohol and 7.41 parts of polyethylene glycol having a molecular weight of approximately 300 were mixed with 18.55 parts of water. To the mixture, 0.01 part of magnesium metasilicate aluminate powder, MgO A1 2SiO (trade name, Neusilin made by FUJI KAGAKU KOGYO, CO., Japan) and 18.52 parts of di-2-hexadecyl adipate (trade name, Eshelan 201 made by Nihon Shono Co.,Japan) were added in order followed by agitation. The mix- :ture was settled over a period of one day. A liquid composition of attractive appearance was obtained wherein small transparent spheres of di-2-hexadecyl adipate were dispersed.

EXAMPLE 3 A liquid composition was prepared in the manner similar to that described in Example 2 from the following ingredients.

Liquid paraffin (viscosity I50 sec/30C, trade name, Union SHP-ZSO made by Union Yushi Co., Japan) 9.90 parts Ethyl alcohol 67.16 Water 23.73 Antimony oxide (fw 2.28) 0.02

The liquid composition so prepared was of attractive appearance wherein relatively small white spheres of liquid paraffin were dispersed.

EXAMPLE 4 A liquid composition was prepared in the manner similar to that described in Example 2 from the following ingredients.

di-2-Hexadecyl adipate 10.0 parts Ethyl alcohol 57.79 Water 32.21 Sodium chloride 0.1

Bismuth oxychloride (indicated in Table l as sample No. 27) 0.02 part EXAMPLE 5 A liquid composition was prepared in the manner similar to that described in Example 2 from the following ingredients.

Liquid paraffin 50.0 parts Ethyl alcohol 41.32 Water 8.68 Sodium chloride 0.1 Fish scale powdcr 0.08

The liquid composition so prepared was of attractive appearance wherein small pearl-like spheres of liquid paraffin were dispersed.

EXAMPLE 6 A liquid composition was prepared in the manner similar to that described in Example 2 from the following ingredients.

di-2-Hexadccyl adipate 47.61 parts Ethyl alcohol 35.68 Water 1 1.93

Polyethylene glycol (molccular weight approximately 300) Magnesium metasilicate aluminate The liquid composition so prepared was of attractive appearance wherein small transparent spheres of di-2- hexadecyl adipate were dispersed, as shown in FIG. 8.

EXAMPLE 7 A liquid composition was prepared in the manner similar to that described in Example 2 from the folb wing ingredients.

Liquid paraffin 24.02 parts Ethyl alcohol 59.17 Water 1 .593 f Bismuth oxychloride 0.07

The liquid composition so prepared was of attractive appearance wherein relatively small pearl-like spheres of liquid paraffin were dispersed, as shown in FIG. 9.

EXAMPLE 8 A liquid composition was prepared in the manner similar to that described in Example 1 from the following ingredients.

Squalanc 10.0 parts Ethyl alcohol 90.0 Bismuth oxychloride 0.01

The liquid composition so prepared was of attractive appearance wherein relatively large pearl-like spheres of squalane were dispersed, as shown in FIG. 10.

EXAMPLE 9 A liquid composition was prepared in the manner similar to that described in Example 2 from the following ingredients.

Liquid paraffin 12.5 parts di-2-Hexadecyl adipate 12.5 Ethyl alcohol 54.87 Water 20.13

Bismuth oxychloride 0.04

The liquid composition so prepared was of attractive appearance wherein small pearl-like spheres of liquid paraffin and di-2-hexadecyl adipate were dispersed, as shown in FIG. 11.

EXAMPLE 10 A liquid composition was prepared in the manner similar to that described in Example 2 from the following ingredients.

di-2-1-1exadecyl adipate 25.0 parts Liquid paraffin 25.0 Ethyl alcohol 36.58 Water 13.42 Nylon 12 (made by Toray Industries lnc., Japan) 0.06

The liquid composition so prepared was attractive appearance wherein relatively small translucent spheres of di-2-hexadecyl adipate and liquid paraffin were dispersed, as shown in FIG. 12.

EXAMPLE 1 l A liquid composition was prepared in the manner similar to that described in Example 2 from the following ingredients.

di-Z-I-lexadecyl adipate 25.0 parts Ethyl alcohol 48.16 Water 26.84 Sodium chloride 0.1

Titanium dioxide powder (particle size,

approximately 30 mp.) 0.01

The liquid composition so prepared was of attractive appearance wherein small translucent spheres of di-2- hexadecyl adipate were dispersed.

EXAMPLE 12 A liquid composition was prepared in the manner similar to that described in Example 2 from the following ingredients.

12 The liquid composition so prepared was of attractive appearance wherein very small translucent spheres of liquid paraffin and oleyl alcohol were dispersed, as shown in FIG. 13.

EXAMPLE 13 A liquid composition was prepared in the manner similar to that described in Example 2 from the following ingredients.

di-2-l-Iexadecyl adipate 18.52 parts Isopropyl alcohol 55.60 Water 18.64 Polyethylene glycol (molecular weight,

approximately 300) 7.41 Magnesium metasilicate aluminate 0.01

The liquid composition so prepared was of attractive appearance wherein small transparent spheres of di-2- hexadecyl adipate were dispersed.

What we claim is:

l. A liquid cosmetic composition of a two phase type, which comprises:

1. up to about by weight of an aqueous phase substantially comprised of water and at least one organic liquid selected from the group consisting of ethyl alcohol, N-methyl pyrrolidone/and isopropyl alcohol,

2. up to about 95% by weight of an oil phase in the form of spheres having diameters of 0.1 mm to 1.0 cm dispersed in said aqueous phase, said oil phase being substantially comprised of at least one'member selected from the group consisting of liquid paraffin, squalane, 2-hexyldecy1 palmitate, 2-octyldodecyl myristate, di-2-hexyldecy1 adipate, di-2- ethylhexyl sebacate, olive oil, tsubaki oil, mink oil, isostearic acid, oleic acid, oleyl alcohol and a polypropyleneglycol butyl ether having a polymerization degree of approximately 40, and

3. not greater than approximately 50% by weight of finely divided solid particles insoluble in the liquid ingredients (1) and (2) set forth above, said solid particles having particle sizes of less than about micron and being adsorbed on the interface between said aqueous phase (1) and said oil phase (2), said solid particle being selected from at least one member selected from the group consisting of talc, kaolin, iron oxide, magnesium oxide, zinc oxide,/zinc peroxide, titanium oxide, precipitated calcium carbonate, calcium secondary phosphate, aluminium hydroxide, antimony oxide, alumina, barium sulfate, silicic acid anhydride, magnesium metasilicate aluminate, silica-alumina, bismuth oxychloride, microcrystalline cellulose, fish scale, polyvinyl chloride and poly-Q-lauryllactam the proportion in the amount of water to the organic liquid in said aqueous phase (1 being such that the difference in specific gravity between said aqueous phase (1) and said oil phase (2) is not greater than 0.04 and wherein a spreading coefficient S defined as having the following formula is negative,

7u: Y0 Yow wherein y and y are surface tensions of the oil and the homogeneous mixture of water and the organic liquid respectively, and 7 is an interfacial tension between 13 the oil and the homogeneous mixture of water and the organic liquid.

2. A liquid comsmetic composition according to claim 1 wherein said oil phase is present in an amount of less than 60% by weight based on the weight of the cosmetic composition.

3. A liquid cosmetic composition of a two phase type, according to claim 1 which consists essentially of:

1. not more than approximately 95% by weight of an aqueous phase substantially comprised of water and at least one organic liquid selected from the group consisting of ethyl alcohol and isopropyl alcohol,

2. less than 60% by weight of an oil phase in the form of spheres of 0.1 mm to 1.0 cm diameter dispersed in said aqueous phase, said oil phase being substantially comprised of at least one member selected from the group consisting of liquid paraffin, di-Z- hexyldecyl adipate, squalane and oleyl alcohol, and

3. not more than approximately 50% by weight of finely divided solid particles insoluble in the liquid ingredients (1) and (2) set forth above, said solid particles having particle sizes smaller than approximately 100 microns and being adsorbed on the interface between said aqueous phase l and said oil phase (2) and being at least one member selected from the group consisting of precipitated calcium carbonate, zinc oxide, zinc peroxide, talc, bentonite, iron oxide, antimony oxide, magnesium metasilicatealuminate, bismuth oxychloride, fish scale and poly-Q-lauryllactam, the proportion in the amount of water to the organic liquid in said aqueous phase 1) being such that the difference in specific gravity between said aqueous phase (1) and said oil phase (2) is not greater than 0.04 and wherein a spreading coefficient S defined as having the following formula is negative,

am-vow wherein y and 7,, are surface tensions of the oil and the homogeneous mixture of water and the organic liquid, respectively, and 7 is an interfacial tension between the oil and the homogeneous mixture of water and the organic liquid.

14 4. A liquid cosmetic composition of a two phase type, according to claim 1 which consists essentially of:

I. not more than approximately by weight of an organic liquid phase comprising at least one member selected from the group consisting of ethyl alcohol and isopropyl alcohol,

2. not more than approximately 95% by weight of an oil phase in the form of spheres of 0.1 mm to 1.0 cm diameter dispersed in said organic liquid phase, said oil phase comprising at least one member selected from the group consisting of liquid paraffin, squalane, 2-hexyldecyl palmitate, 2-octyldodecyl myristate, di-2-hexyldcyl adipate, di-Z-ethylhexyl sebacate, olive oil, tsubaki oil, mink oil, isostearic acid, oleic acid, oleyl alcohol, and a polypropyleneglycol butyl ether having a polymerization degree of approximately 40, and

3. not more than approximately 50% by weight of finely divided solid particles insoluble in the liquid ingredients (1) and (2) set forth above, said solid particles having particle sizes of less than microns approximately and being adsorbed on the interface between said organic liquid phase (1) and said oil phase (2), and being at least one member selected from the group consisting of talc, kaolin, iron oxide, magnesium oxide, zinc peroxide, titanium oxide, precipitated calcium carbonate, calcium secondary phosphate, aluminium hydroxide, antimony oxide, alumina, barium sulfate, silicic acid anhydride, magnesium metasilicatealuminate, silica-alumina, bismuth oxychloride, microcrystalline cellulose, fish scale, pearl, polyvinyl chloride and poly-Q-lauryllactam,

the difference in specific gravity between said organic liquid (1) and said oil (2) being not greater than 0.04

and wherein a spreading coefficient S defined as having the following formula is negative,

yu- 'Yo Yow wherein y and 7 are surface tensions of the oil and the homogeneous mixture of water and the organic liquid, respectively, and y is an interfacial tension between the oil and the homogeneous mixture of water and the organic liquid. 

1. A LIQUID COSMETIC COMPOSITION OF A TWO-PHASE TYPE, WHICH COMPRISES:
 1. UP TO ABOUT 95% BY WEIGHT OF AN AQUEOUS PHASE SUBSTANTIALLY COMPRISED OF WATER AND AT LEAST ONE ORGANIC LIQUID SELECTED FROM THE GROUP CONSISTING OF ETHYL ALCOHOL, NMETHYL PYRROLIDONE/AND ISOPROPYL ALCOHOL,
 2. UP TO ABOUT 95% BY WEIGHT OF AN OIL PHASE IN THE FORM OF SPHERES HAVING DIAMETERS OF 0.1 MM TO 1.0 CM DISPERSED IN SAID AQUEOUS PHASE, SAID OIL PHASE BEING SUBSTANTIALLY COMPRISED OF AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF LIQUID PARAFFIN, SQUALANE, 2-HEXYLDECYL PALMINATE, 2-OCTYLDODECYL MYRISTATE, DI-2-HEXYLDECYL ADIPATE, DI-2- ETHYLHEXYL SEBACATE, OLIVE OIL, TSUBAKI OIL, MINK OIL, ISOSETERIC ACID, OLEIC ACID, OLEYL ALCOHOL AND A POLYPROPYLENEGLYCOL BUTYL ETHER HAVING A POLYMERIZATION DEGREE OF APPROXIMATELY 40, AND
 2. up to about 95% by weight of an oil phase in the form of spheres having diameters of 0.1 mm to 1.0 cm dispersed in said aqueous phase, said oil phase being substantially comprised of at least one member selected from the group consisting of liquid paraffin, squalane, 2-hexyldecyl palmitate, 2-octyldodecyl myristate, di-2-hexyldecyl adipate, di-2-ethylhexyl sebacate, olive oil, tsubaki oil, mink oil, isostearic acid, oleic acid, oleyl alcohol and a polypropyleneglycol butyl ether having a polymerization degree of approximately 40, and
 2. A liquid comsmetic composition according to claim 1 wherein said oil phase is present in an amount of less than 60% by weight based on the weight of the cosmetic composition.
 2. less than 60% by weight of an oil phase in the form of spheres of 0.1 mm to 1.0 cm diameter dispersed in said aqueous phase, said oil phase being substantially comprised of at least one member selected from the group consisting of liquid paraffin, di-2-hexyldecyl adipate, squalane and oleyl alcohol, and
 2. not more than approximately 95% by weight of an oil phase in the form of spheres of 0.1 mm to 1.0 cm diameter dispersed in said organic liquid phase, said oil phase comprising at least one member selected from the group consisting of liquid paraffin, squalane, 2-hexyldecyl palmitate, 2-octyldodecyl myristate, di-2-hexyldecyl adipate, di-2-ethylhexyl sebacate, olive oil, tsubaki oil, mink oil, isostearic acid, oleic acid, oleyl alcohol, and a polypropyleneglycol butyl ether having a polymerization degree of approximately 40, and
 3. not more than approximately 50% by weight of finely divided solid particles insoluble in the liquid ingredients (1) and (2) set forth above, said solid particles having particle sizes of less than 100 microns approximately and being adsorbed on the interface between said organic liquid phase (1) and said oil phase (2), and being at least one member selected from the group consisting of talc, kaolin, iron oxide, magnesium oxide, zinc peroxide, titanium oxide, precipitated calcium carbonate, calcium secondary phosphate, aluminium hydroxide, antimony oxide, alumina, barium sulfate, silicic acid anhydride, magnesium metasilicatealuminate, silica-alumina, bismuth oxychloride, microcrystalline cellulose, fish scale, pearl, polyvinyl chloride and poly- Omega -lauryllactam, the difference in specific gravity between said organic liquid (1) and said oil (2) being not greater than 0.04 and wherein a spreading coefficient S defined as having the following formula is negative, S gamma w- gamma o- gamma ow wherein gamma o and gamma w are surface tensions of the oil and the homogeneous mixture of water and the organic liquid, respectively, and gamma ow is an interfacial tension between the oil and the homogeneous mixture of water and the organic liquid.
 3. not more than approximately 50% by weight of finely divided solid particles insoluble in the liquid ingredients (1) and (2) set forth above, said solid particles having particle sizes smaller than approximately 100 microns and being adsorbed on the interface between said aqueous phase (1) and said oil phase (2) and being at least one member selected from the group consisting of precipitated calcium carbonate, zinc oxide, zinc peroxide, talc, bentonite, iron oxide, antimony oxide, magnesium metasilicatealuminate, bismuth oxychloride, fish scale and poly- Omega -lauryllactam, the proportion in the amount of water to the organic liquid in said aqueous phase (1) being such that the difference in specific gravity between said aqueous phase (1) and said oil phase (2) is not greater than 0.04 and wherein a spreading coefficient S defined as having the following formula is negative, S gamma w- gamma o- gamma ow wherein gamma o and gamma w are surface tensions of the oil and the homogeneous mixture of water and the organic liquid, respectively, and gamma ow is an interfacial tension between the oil and the homogeneous mixture of water and the organic liquid.
 3. A liquid cosmetic composition of a two phase type, according to claim 1 which consists essentially of:
 3. not greater than approximately 50% by weight of finely divided solid particles insoluble in the liquid ingredients (1) and (2) set forth above, said solid particles having particle sizes of less than about 100 micron and being adsorbed on the interface between said aqueous phase (1) and said oil phase (2), said solid particle being selected from at least one member selected from the group consisting of talc, kaolin, iron oxide, magnesium oxide, zinc oxide,/zinc peroxide, titanium oxide, precipitated calcium carbonate, calcium secondary phosphate, aluminium hydroxide, antimony oxide, alumina, barium sulfate, silicic acid anhydride, magnesium metasilicate aluminate, silica-alumina, bismuth oxychloride, microcrystalline cellulose, fish scale, polyvinyl chloride and poly- Omega -lauryllactam the proportion in the amount of water to the organic liquid in said aqueous phase (1) being such that the difference in specific gravity between said aqueous phase (1) and said oil phase (2) is not greater than 0.04 and wherein a spreading coefficient S defined as having the following formula is negative, S gamma w-gamma o- gamma ow wherein gamma o and gamma w are surface tensions of the oil and the homogeneous mixture of water and the organic liquid respectively, and gamma ow is an interfacial tension between the oil and the homogeneous mixture of water and the organic liquid.
 3. NOT GREATER THAN APPROXIMATELY 50% BY WEIGHT OF FINELY DIVIDED SOLID PARTICLES INSOLUBLE IN THE LIQUID INGREDIENTS (1) AND (2) SET FROTH ABOVE, SAID SOLID PARTICLES HAVING PARTICLE SIZES OF LESS THAN ABOUT 100 MICRON AND BEING ADSORBED ON THE INTERFACE BETWEEN SAID AQUEOUS PHASE (1) AND SAID OIL PHASE (2), SAID SOLID PARTICLE BEING SELECTED FROM AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF TALC, KAOLIN, IRON OXIDE, MAGNESIUM OXIDE, ZINC OXIDE,/ZINC PEROXIDE, TITANIUM OXIDE, PRECIPITATED CALCIUM CARBONATE, CALCIUM SECONDARY PHOSPHATE, ALUMINIMUM HYDROXIDE, ANTIMONY OXIDE, ALUMINA, BARIUM SULFATE, SILICIC ACID ANHYDRIDE, MAGNESIUM METASILICATE ALUMINATE, SILICA-ALUMINA, BISMUTH OXYCHLORIDE, MICROCRYSTALLINE CELLULOSE, FISH SCALE, POLYVINYL CHLORIDE AND POLY-$-LAURYLLACTAM THE PROPORTION IN THE AMOUNT OF WATER TO THE ORGANIC LIQUID IN SAID AQUEOUS PHASE (1) BEING SUCH THAT THE DIFFERENCE IN SPECIFIC GRAVITY BETWEEN SAID AQUEOUS PHASE (1) AND SAID OIL PHASE (2) IS NOT GREATER THAN 0.04 AND WHEREIN A SPREADING COEFFICIENT S DEFINED AS HAVING THE FOLLOWING FORMULA IS NEGATIVE,
 4. A liquid cosmetic composition of a two phase type, according to claim 1 which consists essentially of: 